Dehydrofluorination of 245FA to 1234ZE

ABSTRACT

A method of producing a fluoropropane fluoropropene of formula CF 3 CH═CHF, comprising contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated Cr 2 O 3  or Cr/Ni on fluoride alumina, in the presence of an oxygen containing gas, to form a mixture comprising Z-1,3,3,3-tetrafluoropropane Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane, separating the E-1,3,3,3-tetrafluoropropene from the Z-isomer and any unreacted 1,1,1,3,3-pentafluoropropane, if present, and recovering said E-1,3,3,3-tetrafluoropropene.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Reissue of U.S. Pat. No. 9,302,962 B2 issued Apr.5, 2016 that claims priority to U.S. Provisional Application No.62/037,138, filed Aug. 14, 2014.

BACKGROUND INFORMATION

1. Field of the Disclosure

This disclosure relates in general to methods of synthesis offluorinated olefins.

2. Description of the Related Art

The fluorocarbon industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for manyapplications has been the commercialization of hydrofluorocarbon (HFC)compounds for use as refrigerants, solvents, fire extinguishing agents,blowing agents and propellants. These new compounds, such as HFCrefrigerants, HFC-134a and HFC-125 being the most widely used at thistime, have zero ozone depletion potential and thus are not affected bythe current regulatory phase-out as a result of the Montreal Protocol.

In addition to ozone depleting concerns, global warming is anotherenvironmental concern in many of these applications. Thus, there is aneed for compositions that meet both low ozone depletion standards aswell as having low global warming potentials. Certain hydrofluoroolefinsare believed to meet both goals. Thus there is a need for manufacturingprocesses that provide halogenated hydrocarbons and fluoroolefins thatcontain no chlorine that also have a low global warming potential.

HFC-1234yf (CF₃CF═CH₂) and HFC-1234ze (CF₃CH═CHF), both having zeroozone depletion and low global warming potential, have been identifiedas potential refrigerants. U.S. Patent Publication No. 2006/0106263 A1discloses the production of HFC-1234yf by a catalytic vapor phasedehydrofluorination of CF₃CF₂CH₃ or CF₃CHFCH₂F, and of HFC-1234ze(mixture of E- and Z-isomers) by a catalytic vapor phasedehydrofluorination of CF₃CH₂CHF₂.

The catalytic dehydrofluorination of hydrofluorocarbons to producehydrofluoroolefins is ordinarily carried out in the vapor phase using adehydrofluorination catalyst. Vapor phase dehydrofluorination catalystsare well known in the art. These catalysts include, but are not limitedto, alumina, aluminum fluoride, fluorided alumina, metal compounds onaluminum fluoride, metal compounds on fluorided alumina; chromiumoxides, fluorided chromium oxides, and cubic chromium trifluoride;oxides, fluorides, and oxyfluorides of magnesium, zinc and mixtures ofmagnesium and zinc and/or aluminum; lanthanum oxide and fluoridedlanthanum oxide; carbon, acid-washed carbon, activated carbon, threedimensional matrix carbonaceous materials; and metal compounds supportedon carbon. The metal compounds are oxides, fluorides, and oxyfluoridesof at least one metal selected from the group consisting of sodium,potassium, rubidium, cesium, yttrium, lanthanum, cerium, praseodymium,neodymium, samarium, chromium, iron, cobalt, rhodium, nickel, copper,zinc, and mixtures thereof. In the alternative, dehydrofluorinations canbe carried out in the liquid phase through reaction with aqueous oralcohol solutions of caustic, such as potassium hydroxide, or sodiumhydroxide.

Catalytic dehydrofluorination of HFC-245fa in general produces a mixtureof both the E-isomer as well as the Z-isomer of HFC-1234ze. Depending onthe particular catalyst chosen, the amount of the Z-isomer can varybetween 15 to 23%. Dehydrofluorination in the liquid phase using aqueoussolutions of caustic or other strong bases also produces mixture of bothisomers. Although the ratio of the two isomers can be shifted somewhatby temperature, about 13-15% of the Z-isomer is typically formed. As theE-isomer is the most useful for refrigeration applications, afterseparation of the E-isomer from the Z-isomer, the Z-isomer is typicallyeither isomerized to the E-isomer in a separate step, or converted backto 245fa through addition of hydrogen fluoride. Both alternativesrequire additional steps which add cost.

There is a continuing need for more selective and efficientmanufacturing processes for the production of HFC-1234ze and HFC-1234yf.

SUMMARY

Described is a method of producing a fluoropropane fluoropropene offormula CF₃CH═CHF, comprising contacting a mixture of1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene in thegas phase with a catalyst comprising at least one catalyst selected fromthe group consisting of fluorinated Cr₂O₃ or Cr/Ni on fluorided alumina,optionally in the presence of an oxygen containing gas, to form amixture comprising Z-1,3,3,3-tetrafluoropropaneZ-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene, andoptionally unreacted 1,1,1,3,3-pentafluoropropane, separating theE-1,3,3,3-tetrafluoropropene from the Z-isomer and any unreacted1,1,1,3,3-pentafluoropropane, if present, and returning saidZ-1,3,3,3-tetrafluoropropene to be fed to the reactor with additional1,1,1,3,3-pentafluoropropane.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

DETAILED DESCRIPTION

Described is a method of producing a fluoropropane fluoropropene offormula CF₃CH═CHF, comprising contacting a mixture of1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene in thegas phase with a catalyst comprising at least one catalyst selected fromthe group consisting of fluorinated Cr₂O₃ or Cr/Ni on fluoride alumina,optionally in the presence of an oxygen containing gas, to form amixture comprising Z-1,3,3,3-tetrafluoropropaneZ-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene, andoptionally unreacted 1,1,1,3,3-pentafluoropropane, separating theE-1,3,3,3-tetrafluoropropene from the Z-isomer and any unreacted1,1,1,3,3-pentafluoropropane, if present, and returning saidZ-1,3,3,3-tetrafluoropropene to be fed to the reactor with additional1,1,1,3,3-pentafluoropropane.

Dehydrofluorination reactions are well known in the art. Thedehydrofluorination of HFC-245fa has been particularly studied. Both gasphase and liquid phases processes are known. 1,3,3,3-Tetrafluoropropene(HFO-1234ze) exists as both a Z-isomer and an E-isomer about the doublebond. Both gas phase and liquid phase processes are known to produce amixture of both the Z- and E-isomers, with the E-isomer predominating.The selectivity for the production of the Z-isomer can vary from about10% to about 23%, depending on the temperature, and choice of catalyst.The boiling point of the E-isomer at 1 atm is about −19 C, while theboiling point of the Z-isomer is about +9 C. For many uses, the E-isomeris preferred. So as to minimize yield losses in the form of thegenerally unwanted Z-isomer, it becomes necessary to either add anisomerization step to isomerize the Z-isomer to the E-isomer, or add afluorination step to convert Z-1234ze back to HFC-245fa.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims.

Dehydrofluorinations are known in the art, and are preferably conductedin the vapor phase. The dehydrofluorination reaction may be conducted inany suitable reaction vessel or reactor, but it should preferably beconstructed from materials which are resistant to the corrosive effectsof hydrogen fluoride, such as nickel and it's alloys, includingHastelloy, Monel, and Inconel, or vessels lined with fluoropolymers.These may be a single tube, or multiple tubes packed with adehydrofluorination catalyst.

Useful catalysts for the process include chromium-based catalysts suchas fluorided chromium oxide, which catalyst may either be unsupported,or supported on a support such as activated carbon, graphite, fluoridegraphite, or fluorided alumina. The chromium catalyst may either be usedalone, or in the presence of a co-catalyst selected from nickel, cobalt,manganese or zinc salt. In one embodiment, a chromium catalyst is highsurface area chromium oxide, or chromium/nickel on fluoride alumina(Cr/Ni/AlF₃), the preparation of which is reported in European Patent EP486,333. In another embodiment, the catalyst is fluorided Guignet'sgreen catalyst. The chromium catalysts are preferably activated beforeuse, typically by a procedure whereby the catalyst is heated to from 350to 400° C. under a flow of nitrogen for a period of time, after whichthe catalyst is heated under a flow of HF and nitrogen or air for anadditional period of time.

In one embodiment, the Guignet's Green of the fluoride-activatedGuignet's Green catalyst used in the present invention is made byreacting (fusing) boric acid with alkali metal dichromate at 500° C. to800° C., followed by hydrolysis of the reaction product, whereby saidGuignet's Green contains boron, alkali metal, and water of hydration.The usual alkali metal dichromates are the Na and/or K dichromates. Thereaction is typically followed by the steps of cooling the reactionproduct in air, crushing this solid to produce a powder, followed byhydrolysis, filtering, drying, milling and screening. The Guignet'sGreen is bluish green, but is known primarily as a green pigment,whereby the pigment is commonly referred to as Guignet's Green. Whenused as a catalyst, it is also referred to as Guignet's Green asdisclosed in U.S. Pat. No. 3,413,363. In U.S. Pat. No. 6,034,289, Cr₂O₃catalysts are disclosed as preferably being in the alpha form, andGuignet's Green is also disclosed as a commercially available greenpigment having the composition: Cr₂O₃ 79-83%, H₂O 16-18 wt %, B₂O₅ 1.5to 2.7% (sentence bridging cols. 2 and 3) that can be converted to thealpha form (col. 3, I. 3). U.S. Pat. No. 7,985,884 acknowledges thepresence of alkali metal in the Guignet's Green in the composition ofGuignet's Green disclosed in Example 1: 54.5% Cr, 1.43% B, 3400 ppm Na,and 120 ppm K.

The physical shape of the catalyst is not critical and may, for example,include pellets, extrudates, powders, or granules. The fluorideactivation of the catalyst is preferably carried out on the final shapeof the catalyst.

In one embodiment, the current inventors have discovered that feeding amixture of HFC-245fa and at least about 10% by weight of the Z-isomer ofHFO-1234ze to a dehydrofluorination reactor in the presence of an oxygencontaining gas can suppress the formation of additional Z-isomer so thatthe HFC-245fa converted by dehydrofluorination produces substantiallyonly E-HFO-1234ze. Feeding less than about 10% will result in somesuppression of the formation of additional Z-1234ze. Feeding greaterthan about 10% by weight of Z-1234ze simply results in the presence ofadditional material which must be separated and recycled. The amount ofZ-1234ze which is necessary to suppress the further formation ofZ-isomer product is dependent to some extent on conversion. At 70%conversion of 245fa, about 10-11% Z-isomer in the feed is required. At80% conversion, about 13% Z-isomer in the feed is required.

In one embodiment, the reaction vessel can be held at a temperature ofbetween 200° C. and 375° C. In another embodiment, the reaction vesselcan be held at a temperature of between 250° C. and 350° C. In yetanother embodiment, the reaction vessel can be held at a temperature ofbetween 275° C. and 325° C.

The reaction pressure can be subatmpospheric, atmospheric orsuperatmostpheric. In one embodiment, the reaction is conducted at apressure of from 14 psig to about 100 psig. In another embodiment, thereaction is conducted at a pressure of from 14 psig to about 60 psig. Inyet another embodiment, the reaction is conducted at a pressure of from40 psig to about 85 psig. In yet another embodiment, the reaction isconducted at a pressure of from 50 psig to 75 psig. In general,increasing the pressure in the reactor above atmospheric pressure willact to increase the contact time of the reactants in the process. Longercontact times will necessarily increase the degree of conversion in aprocess, without having to increase temperature.

Depending on the temperature of the reactor, and the contact time, theproduct mixture from the reactor will contain varying amounts ofunreacted HFC-245fa. E-1,3,3,3-tetrafluoropropene is then separated fromthe Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and any unreactedHFC-245fa, which are then recycled back to the reactor with additionalHFC-245fa. Hydrogen fluoride may be removed by scrubbing, by passing thereactor effluent through a solution of aqueous caustic, or hydrogenfluoride may be removed by distillation.

In one embodiment, the reactor feed is preheated in a vaporizer to atemperature of from about 30° C. to about 100° C. In another embodiment,the reactor feed is preheated in a vaporizer to a temperature of fromabout 30° C. to about 80° C.

In some embodiments, an inert diluent gas is used as a carrier gas forthe hydrochlorofluoropropane. In one embodiment, the carrier gas isselected from nitrogen, argon, helium or carbon dioxide.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole. Thetransitional phrase “consisting essentially of” is used to define acomposition, method that includes materials, steps, features,components, or elements, in addition to those literally disclosedprovided that these additional included materials, steps, features,components, or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention, especially the mode ofaction to achieve the desired result of any of the processes of thepresent invention. The term ‘consisting essentially of’ occupies amiddle ground between “comprising” and ‘consisting of’.

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis citedIn case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

Example 1 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Johnson Mathey) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 1.

TABLE 1 % Z-ze added 0 7.5 10.9 Incoming compos 100/0 92.5/7.5 89/11245fa conversion (%) 71.2 69.3 72 Z-ze in product (%) 10.7 10.3 11.2 %recovered 245fa 28.8 28.4 24.9 % E-ze 60.5 60.3 63.9 % yield E-ze 60.565.3 71.7 % selectivity E-ze 85 94.2 99.7

Example 2

Example 2 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Guignet's green) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 2.

TABLE 2 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 69.9 71.8 Z-ze in product (%) 10.7 10.9 % recovered 245fa 30.1 25.1% E-ze 59.2 64 % yield E-ze 59.2 71.9 % selectivity E-ze 84.7 100

Example 3

Example 3 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Johnson Mathey) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 3.

TABLE 3 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 73 71.3 Z-ze in product (%) 11.4 11.0 % recovered 245fa 27.0 25.5 %E-ze 61.6 63.5 % yield E-ze 61.6 72.5 % selectivity E-ze 84 100

Example 4

Example 4 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Newport Cr) which had been prepared as follows. Chromic oxidein extrudate form, which was crushed and sieved to 12/20 mesh. Aftercharging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 4.

TABLE 4 % Z-ze added 0 10.7 Incoming compos 100/0 89.3/10.7 245faconversion (%) 72.2 70.2 Z-ze in product (%) 10.4 10.5 % recovered 245fa27.8 26.6 % E-ze 61.8 62.9 % yield E-ze 61.8 70.4 % selectivity E-ze85.5 100

Example 5

Example 4 demonstrates the dehydrofluorination of 245fa over fluoridedalumina in the presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) is filled with 10 cc (6.1 gm) of Al2O3catalyst (purchased from Sigma-Aldrich). Al2O3 in extrudate form, whichis crushed and sieved to 12/20 mesh. After charging the reactor tube,the temperature of the catalyst bed is raised to 300° C. and purged withnitrogen (30 cc/min) for 200 minutes. Then the flow of nitrogen isreduced to 60 cc/min and HF is fed at 20 cc/min for 60 minutes. Thetemperature is increase to 325° C. for 300 minutes. The flow of nitrogenis then lowered to 30 cc/min and the flow of HF is raised to 30 cc/minfor 30 minutes. The flow of nitrogen is then lowered to 12 cc/min andthe flow of HF is raised to 48 cc/min for 60 minutes. The flow ofnitrogen is then discontinued and the flow of HF is raised to 48 cc/minfor 30 minutes. The reactor temperature is then decreased to 250° C. for30 minutes. Afterwards HF is turned off and the reactor is purged with30 cc/min of nitrogen. The reactor temperature is then stabilized at300° C., the flow of nitrogen is turned off, and either CF₃CH₂CHF₂, orCF₃CH₂CHF₂ with varying amounts of Z-1234ze, is fed at 1.44 ml/hr.Contact time in the reactor is 45 seconds. The CF₃CH₂CHF₂ is vaporizedat 50° C. Part of the reactor effluent is passed through a series ofvalves and analyzed by GCMS. Amounts for Z-1234ze, 245fa and E-1234zeare expressed as mole percent. Results are summarized in Table 5.

TABLE 5 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 70 71 Z-ze in product (%) 11 11 % recovered 245fa 30 29 % E-ze 59 58% yield E-ze 59 65 % selectivity E-ze 84.3 100

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges include each and everyvalue within that range.

What is claimed is:
 1. A method of producing a fluoropropanefluoropropene of formula CF₃CH═CHF while suppressing additionalproduction of Z-1,3,3,3-tetrafluoropropene, comprising: a) providing andcontacting a starting feed mixture of 1,1,1,3,3-pentafluoropropane andat least 10% by weight Z-1,3,3,3-tetrafluoropropene to suppress itsproduction in the gas phase with a catalyst comprising at least onecatalyst selected from the group consisting of fluorinated Cr₂O₃ orCr/Ni on fluorided alumina, in the presence of an oxygen containing gas,to form a product mixture comprising Z-1,3,3,3-tetrafluoropropaneZ-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene, hydrogenfluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane, b)separating the E-1,3,3,3-tetrafluoropropene from the Z-isomer and anyunreacted 1,1,1,3,3-pentafluoropropane, if present, and c) recoveringsaid E-1,3,3,3-tetrafluoropropene.
 2. The method of claim 1, whereinsaid mixture of 1,1,1,3,3-pentafluoropropane andZ-1,3,3,3-tetrafluoropropene comprises at least 7% by weightZ-1,3,3,3-tetrafluoropropene.
 3. The method of claim 1, wherein saidmixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropenecomprises at least 10% by weight Z-1,3,3,3-tetrafluoropropene.
 4. Themethod of claim 1, wherein at least 94% the isomeric selectivity of theconversion of the 1,1,1,3,3-pentafluoropropane is converted to E-isomerof 1,3,3,3-tetrafloropropene 1,3,3,3-tetrafluoropropene is at least 94mol %.
 5. The method of claim 1, wherein at least 98% the isomericselectivity of the conversion of the 1,1,1,3,3-pentafluoropropane isconverted to E-isomer of 1,3,3,3-tetrafloropropene1,3,3,3-tetrafluoropropene is at least 98 mol %.
 6. The method of claim1, further comprising recovering Z-1,3,3,3-tetrafluoropropene, or amixture of Z-1,3,3,3-tetrafluoropropene and1,1,1,3,3-pentafluoropropane, and recyclingZ-1,3,3,3-tetrafluoropropene, or a mixture ofZ-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane back tostep a).
 7. The process method of claim 1, wherein said hydrogenfluoride produced in step a) is separated and recovered.
 8. The processmethod of step claim 1, wherein said oxygen containing gas is oxygen, orair.
 9. The method of claim 8, wherein said oxygen containing gas isoxygen.
 10. The method of claim 9, further providing theE-1,3,3,3-tetrafluoropropene to a refrigerant system.
 11. A methodcomprising: a) contacting a starting feed mixture of1,1,1,3,3-pentafluoropropane and at least 10% by weightZ-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst comprisingat least one catalyst selected from the group consisting of fluorinatedCr₂O₃ or Cr/Ni on fluorided alumina, in the presence of an oxygencontaining gas in a reactor, to suppress additional formation of theZ-1,3,3,3-tetrafluoropropene and form a reactor product mixturecomprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene,hydrogen fluoride, and optionally unreacted1,1,1,3,3-pentafluoropropane, b) separating theE-1,3,3,3-tetrafluoropropene from the Z-isomer and any unreacted1,1,1,3,3-pentafluoropropane, if present, and c) recovering saidE-1,3,3,3-tetrafluoropropene and providing theE-1,3,3,3-tetrafluoropropene to a refrigerant system.
 12. The method ofclaim 11, the method including operating the refrigerant system, whereinthe refrigerant system comprises the E-1,3,3,3-tetrafluoropropene. 13.The method of claim 1, wherein said mixture of1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene comprisesat least 11% by weight Z-1,3,3,3-tetrafluoropropene.
 14. The method ofclaim 12, wherein the isomeric selectivity of the conversion of the1,1,1,3,3-pentafluoropropane to E-isomer of 1,3,3,3-tetrafluoropropeneis at least 94 mol %.
 15. The method of claim 12, wherein the isomericselectivity of the conversion of the 1,1,1,3,3-pentafluoropropane toE-isomer of 1,3,3,3-tetrafluoropropene is at least 98 mol %.
 16. Themethod of claim 12, further comprising recoveringZ-1,3,3,3-tetrafluoropropene, or a mixture ofZ-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, andrecycling Z-1,3,3,3-tetrafluoropropene, or a mixture ofZ-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane back tostep a).
 17. The process of claim 12, wherein said hydrogen fluorideproduced in step a) is separated and recovered.
 18. The process of claim12, wherein said oxygen containing gas is oxygen, or air.
 19. The methodof claim 10, further comprising operating the refrigerant system, therefrigerant system comprising said E-1,3,3,3-tetrafluoropropenerecovered.
 20. The method of claim 1, wherein the isomeric selectivityof the 1,3,3,3-tetrafluoropropene as directly formed from the1,1,1,3,3-pentafluoropropane is at least 99.7 mol % E-isomer.
 21. Themethod of claim 11, wherein the isomeric selectivity of the1,3,3,3-tetrafluoropropene as directly formed from the1,1,1,3,3-pentafluoropropane is at least 99.7 mol % E-isomer.
 22. Themethod of claim 1, wherein the contacting is conducted at a temperatureheld between 275° C. and 350° C.
 23. The method of claim 11, wherein thecontacting is conducted at a temperature held between 275° C. and 350°C.
 24. The method of claim 1, wherein the product mixture includes amole ratio of E-1,3,3,3-tetrafluoropropene toZ-1,3,3,3-tetrafluoropropene of about 5.7 to about
 6. 25. The method ofclaim 11, wherein the product mixture includes a mole ratio ofE-1,3,3,3-tetrafluoropropene to Z-1,3,3,3-tetrafluoropropene of about5.7 to about 6.